WO1991001879A1 - Stratifie composite thermoplastique autorenforce - Google Patents

Stratifie composite thermoplastique autorenforce Download PDF

Info

Publication number
WO1991001879A1
WO1991001879A1 PCT/US1990/004463 US9004463W WO9101879A1 WO 1991001879 A1 WO1991001879 A1 WO 1991001879A1 US 9004463 W US9004463 W US 9004463W WO 9101879 A1 WO9101879 A1 WO 9101879A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
composite
liquid crystal
matrix
fibers
Prior art date
Application number
PCT/US1990/004463
Other languages
English (en)
Inventor
Avraam I. Isayev
Original Assignee
University Of Akron
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by University Of Akron filed Critical University Of Akron
Publication of WO1991001879A1 publication Critical patent/WO1991001879A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/12—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/706—Anisotropic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/708—Isotropic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/26—Composite fibers made of two or more materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249942—Fibers are aligned substantially parallel
    • Y10T428/249947—Polymeric fiber
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/24995—Two or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
    • Y10T428/31797—Next to addition polymer from unsaturated monomers

Definitions

  • This invention relates to composite laminates of fiber reinforced thermoplastic materials. More particularly, this invention relates to fiber reinforced thermoplastic laminates in which the reinforcing fibers are formed in situ in a matrix of thermoplastic polymer.
  • Fiber reinforced thermoplastics are well known. Reinforcing fibers may be short (e.g. chopped fiberglass) or long continuous fibers.
  • Cogswell "The Processing Science of Thermoplastic structural Composites", Intern. Polymer Processing, 1 (1987) 4, pp. 157-165 illustrates the latter. Specifically, Cogswell describes polyether etherketone (PEEK) reinforced with carbon fibers. Cogswell further teaches that the composite may be in the form of a laminate of two or more layers or plies, and that the carbon fibers in adjacent layers may be oriented in different directions. Carbon fibers are formed separately and are thereafter incorporated into the thermoplastic matrix by conventional means.
  • PEEK polyether etherketone
  • U.S. Patent Nos. 4,728,698 and 4,835,047 both to Isayev, et al., disclose liquid crystal fiber reinforced polymer composites in which the liquid crystal fibers are formed in situ in a matrix of flexible chain thermoplastic polymer.
  • the essentially unidirectionally oriented fibers are formed by application of high shearing forces with a suitable mixer.
  • This invention according to one aspect provides a shaped reinforced thermoplastic composite formed from a plurality of sheets of self-reinforced thermoplastic material, each sheet comprising long, essentially unidirectionally oriented fibers of a liquid crystal polymer in a matrix of a thermoplastic polymer, said fibers being formed in situ in said matrix under fiber-forming conditions.
  • This invention according to another aspect provides a process for preparing a shaped reinforced thermoplastic composite. This process comprises:
  • each sheet comprising lo g, essentially unidirectionally oriented fibers of a liquid crystal polymer in a matrix of a thermoplastic polymer, said fibers being formed in situ in said matrix under fiber-forming conditions;
  • the shaped reinforced thermoplastic composite may be a composite laminate, and the invention will be described with particular reference thereto.
  • the lay-up may be formed so that the fibers in the individual sheets or layers are oriented either in the same direction or in different directions.
  • the resulting composite will be anisotropic, i.e., mechanical properties in the fiber direction will be different from the corresponding properties in other directions.
  • an essentially isotropic composite is attained.
  • Fig. 1 is a schematic isometric view of a composite laminate according to one embodiment of the invention, in which the direction of fiber orientation in all layers is the same.
  • Fig. 1A is a schematic isometric representation of a composite laminate according to a second embodiment of the invention, in which the fibers in different layers are oriented in different directions so as to give an essentially isotropic composite laminate.
  • Fig. 2 is a schematic view of the process and apparatus for forming a prepreg in the form of an individual layer or sheet according to this invention.
  • Fig. 3 is a front elevational view of a "coat hanger" sheet-forming die used in the process of this invention.
  • Fig. 3A is a bottom view, looking up, of the die shown in Fig. 3.
  • Fig. 4 is a fragmentary isometric view of a prepreg in the form of an individual sheet according to this invention, showing fiber orientation and also showing by dotted lines a pattern for transverse cutting of this sheet.
  • Fig. 4A is similar to Fig. 4 except that the dotted lines show a pattern for diagonal cutting of the sheet.
  • Figs. 5A, 5B and 5C are schematic diagrams showing various prepregged layups for producing a composite laminate. These differ in the different patterns of fiber orientation with respect to the respective sheet edges and with respect to adjacent sheets or layers.
  • Fig. 6 is a diagrammatic view of a molding machine used in the practice of this invention.
  • Laminate 10 comprises a plurality of layers, including layers 12, 14, 16 and 18. Additional layers (not shown in detail in Fig. 1) may be present.
  • Each layer comprises a plurality of liquid crystal polymer (LCP) fibers 20, which are essentially unidirectionally oriented, in a matrix 22 of a thermoplastic polymer.
  • LCP liquid crystal polymer
  • These fibers 20 are formed in situ in the matrix under fiber-fo ⁇ ing conditions to be hereinafter described.
  • the fibers 20 in all of the layers in the embodiment of Fig. 1 are oriented in the same direction, i.e., the lengthwise direction (parallel to the lengthwise edge of the laminate) .
  • the laminate shown herein is square, so that one edge is arbitrarily taken as the lengthwise edge. Of course, it will be understood that the laminate may be of rectangular or other desired shape.
  • Each layer in- laminate 10 is obtained from an individual prepreg sheet by conventional shaping techniques to be described hereinafter. Thickness of laminate 10 is appreciably less than the total thickness of the prepreg sheets prior to shaping. Laminate 10 of any desired thickness can be obtained simply by choice of the number of prepreg sheets used to prepare the laminate.
  • Fig. 1A shows a composite laminate 10A having a plurality of layers 12A, 14A, 16A and 18A, plus additional layers not shown in detail as desired.
  • Each layer comprises a plurality of essentially unidirectionally oriented long LCP fibers 20 in a matrix 22 of thermoplastic polymer.
  • fibers 20 in different layers of this composite laminate are oriented in different directions, e.g., at 0 degrees, 45 degrees, 90 degrees and 135 degrees (i.e., minus 45 degrees) with respect to the lengthwise edge of the laminate 10A (other suitable fiber orientation patterns will be discussed subsequently) .
  • the fiber orientation pattern shown in the first 4 layers of 12A, 14A, 16A and 18A may repeat throughout the laminate.
  • a fiber orientation pattern such as that shown in Fig. 1A gives an essentially isotropic laminate, i.e., one whose mechanical properties are essentially the same in both the lengthwise and widthwise directions. But in contrast, the laminate 10 of Fig. 1 is anisotropic, displaying different mechanical properties, such as greater ultimate strength and higher modulus in the direction of fiber orientation than in the direction transverse thereto.
  • the required starting materials for preparing the novel composite laminates of this invention are a thermoplastic matrix (or base) polymer and a liquid crystal polymer (LCP) .
  • An LCP herein is in accordance with the art-recognized definition, i.e., a polymer which is anisotropic even in the liquid phase.
  • the matrix polymer is a flexible chain polymer, i.e., one in which successive units of the polymer chain are free to rotate with respect to each other, so that the polymer chain can assume a random shape.
  • the matrix polymer is either amorphous or semi-crystalline.
  • Suitable matrix polymers for this invention include conventional thermoplastic material such as polyethylene, polypropylene, ethylene-propylene copolymers, polystyrene and styrene co-polymers, polyvinyl chloride (PVC) , polyamide (nylon) , polyesters such as polyethylene terephthaiate, polyether etherketone (PEEK) , polyphenylene sulfide, polyetheri ide, polybutylene terephthalate, and polycarbonate.
  • PVC polyvinyl chloride
  • nylon polyamide
  • polyesters such as polyethylene terephthaiate, polyether etherketone (PEEK) , polyphenylene sulfide, polyetheri ide, polybutylene terephthalate, and polycarbonate.
  • PEEK polyether etherketone
  • polyphenylene sulfide polyetheri ide
  • polybutylene terephthalate polycarbonate
  • the liquid crystal polymer (LCP) is a polymer which exhibits anisotropy (i.e., "crystallinity") in the liquid phase.
  • the liquid crystal polymers used in this invention are thermotropic, (i.e., they have a melting point and are melt processable) .
  • the base polymer and the LCP must have an overlapping melt processing temperture range, and the melting point of the LCP must be above the melting point of a semicrystalline base polymer or above the glass transition temperature of an amorphous base polymer.
  • the liquid crystal polymer has a melting point higher than the minimum melt processing temperature of the base or matrix polymer.
  • thermotropic liquid crystal polyme starting materials are the wholly aromatic co-polyesters such as those described in U.S. Patent Nos. 3,991,014; 4,067,852; 4,083,829; 4,130,545; 4,161,470; 4,318,842; and 4,468,364.
  • the LCP must be incompatible with the matrix polymer. That is, addition of the LCP to the base polymer has little or no effect on the glass transition temperature (Tg) or the melting point of the base polymer.
  • Tg glass transition temperature
  • all thermoplastic polymers are classified either as amorphous or semi-crystalline, since as far as the inventor is aware no thermoplastic polymer is completely crystalline. Thus, the polymers which are referred to as "crystalline" iy the published literature would be classified as semi-crystalline herein.
  • polyetherimide PEI
  • a wholly aromatic co-polyester thermotropic liquid crystal polymer having a melting point of about 275°C and supplied by Celanese Research Company, Summit, New Jersey, under the designation "Vectra A 950". This polymer is believe to consist essentially of about
  • Another wholy aromatic copolyester LCP consists of p-oxybenzoyl moieties and oxybiphenylene terephthaloyl moieties, and is available commercially under the tradename "Xydar” from Amoco Company, Chicago, Illinois.
  • Another series of particular suitable composites according to this invention are those made from PEEK as the base polymer and the aforesaid "Xydar" as the liquid crystal polymer.
  • the amount of liquid crystal polymer in a composite laminate 10 or 10A of this invention is preferably from about 40 to about 95 percent by weight of LCP, preferably about 50 to about 90 percent of LCP, balance essentially thermoplastic matrix polymer.
  • the LCP can be formed in situ into fibers in a matrix of the thermoplastic base polymer, under processing conditions which will be described below.
  • composites within this composition range have outstanding mechanical properties. While the desired range of LCP content may vary depending on the particular base polymer and the particular LCP selected, the indicated range of 40-95 percent by weight of LCP is suitable with the preferred thermotropic co-polyester LCP's and the preferred high performance or engineering thermoplastic base materials, such as PEL
  • Additional materials are not required but may be present.
  • an additional reinforcing fiber such as glass, carbon or aramide
  • the additional reinforcing fiber may be incorporated into either the base polymer or the liquid crystal polymer.
  • the additional reinforcement provided by the additional fiber is not necessary in most cases, but where a very high stiffness (or very high strength) reinforced polymer composite is desired, such can be attained according to the present invention without the high loadings of conventional reinforcing fiber required in presently known polymer/fiber composites.
  • additives such as pigments and fillers, coupling agents, flame retardants, lubricants, mold release agents, plasticizers and ultraviolet stabilizers, may be mixed with the base polymer and liquid crystal polymer as desired.
  • the use of such additives is well known in the polymer processing art.
  • the matrix polymer and the liquid crystal polymer are mixed at a temperature at which both are processable by suitable means which will assure thorough mixing of the two polymers. Any additional ingredients which are desired in the final product are also mixed in at this time.
  • the mixing apparatus 30 may comprise, for example, an extruder followed by a static mixer. This extruder may be either a single screw extruder or a twin screw extruder.
  • a particularly suitable extruder 30 for the practice of this invention is a Killion one inch single screw extruder, sold by Killion Extruders, Inc. of Riviera Beach, Florida. Other suitable extruders (disclosed in U.S. Patent Nos.
  • 4,728,698 and 4,835,047) include a ZFK 30 twin screw extruder, sold by Werner & Pfleiderer Corp * of Ramsey, New Jersey.
  • the extruder may be followed by a static mixture (not shown) such as a 6-element Koch Model No. KMB-150 static mixter, made and sold by Koch Industries.
  • the extruder (and the static mixture when used) must be provided with a heating jacket, preferably one which permits zoned heating, so that the matrix polymer and the LCP may be heated from ambient temperature to processing temperature.
  • the base polymer, liquid crystal polymer, and any additional ingredients are fed in solid form to the mixing apparatus such as extruder 30.
  • the base polymer and the liquid crystal polymer are conveniently fed in the form of pellets. These pellets may be either a mixture of pure base polymer pellets and pure LCP pellets, or polymer blend pellets.
  • the processing temperature in extruder 30 is a temperature at which both polymers are melt processable. This is a temperature above the glass transition temperature or melting point, as the case may be, of the matrix polymer and above the melting point of the LCP.
  • the melt blend of LCP and base polymer is passed from the extruder 30 to a sheet forming die 32, shown herein as a "coat hanger" die, where it is subjected to high deformation conditions resulting in fiber formation in situ.
  • Die 32 shown in detail in Fig. 3 and 3A, comprises an inlet 42, a housing 44, which surrounds a cavity 46, and a discharge slit 48 along its lower edge.
  • Discharge slit 48 is long and narrow and preferably adjustable.
  • the polymer blend as it exits from die 32 is in the form of a thin sheet and its dimensions are essentially the same as the dimensions of the slit 48.
  • This thin sheet is passed successively over a first roll 34 and a second roll 36, both of which may be either stationary rolls or rotatable idler rolls. Then the sheet passes through the nip of a pair of rolls 38, which consist of a pair of closely spaced motor driven counter rotating rolls having a pre-determined clearance therebetween.
  • Rolls 38 are driven at a faster speed than that of the sheet emerging from die 32, so that stretching or drawing of the continuous sheet of polymer blend takes place. This stretching or drawing results in essentially uniform orientation of the fibers 20 of LCP's which are contained in the matrix polymer.
  • the extension ratio (also known as “stretch ratio” or “draw ratio”) in the process herein is the ratio of the driven speed of rolls 38 to that of the sheet emerging from die 32.
  • An extension ratio according to this invention should be from about 1.5 to about 5. While these limits may vary, it is necessary to use an extension ratio high enough to result in essentially uniform fiber direction on the one hand, while not so high as to cause the formation of holes in sheet 50 on the other. Actually, it is believed that a combination of extruder temperature and extension ratio (the former must not be too low and the latter must not be too high) , rather than extension ratio alone, is responsible for hole formation in the continuous sheet 50.
  • this continuous sheet 50 is wound up on a motor driven wind-up roll 40.
  • Prepreg sheet 50 is cut into square or rectangular pieces, either transversely along dotted lines 52 shown in Fig. 4, or diagonally (at a 45 deg. angle to the edges) along dotted lines 54 as shown in Fig. 4A.
  • Square pieces are shown for the purpose of illustration.
  • Transverse cutting as showed in Fig. 4 forms pieces 56 in which the direction of fibers 20 is parallel to one edge of the piece.
  • Cutting diagonally as shown in Fig. 4A results in pieces 58 in which the direction of orientation of fibers 20 as at 45 degree angles with respect to the edges or the piece.
  • a prepreg lay-up is formed as shown in Figs. 5 through 5C.
  • a prepreg lay-up is produced by stacking a plurality of prepreg sheets 56 or 58 in a desired pattern, as shown in Figs. 5 through 5C.
  • a first pattern shown in Fig. 5
  • a plurality of sheets 56 in which the fibers 20 extend parallel to two opposite edges, are laid up so that the fibers 20 in every sheet 56 are oriented in the same direction.
  • This results in a lay-up 60 consisting of uncompressed individual sheets 56 in which all fibers 20 are oriented in essentially the same direction.
  • This laminate 60 upon shaping, produces an anisotropic coherent composite laminate 10 as shown in Fig. 1, in which the fibers 20 throughout the laminate are oriented in essentially the same direction.
  • Figs. 5A, 5B and 5C Other lay-up patterns are shown in Figs. 5A, 5B and 5C.
  • sheets 56 (fibers 20 oriented parallel to opposite edges) and 58 (fibers oriented diagonally at a 45 degree angle) are laid up in alternating sequence, resulting in a lay-up 60A of uncompressed sheets in which there are four different fiber directions, i.e., at angles of 0, 45 degree, 90 degree and 135 degree (minus 45 degree) with respect to the lengthwise extending edges of the lay-up (in the case of the square lay-up, one pair of edges is arbitrarily chosen as the lengthwise extending edges) .
  • This lay-up 60A when molded, gives an essentially isotropic composite laminate 10A as shown in Fig. 1A. Since the fibers in this composite laminate 10A extend in different directions which are evenly spaced around the circumference of the circle, the laminate is essentially isotropic, which means that the mechanical properties and either the length direction or the width direction are essentially the same.
  • essentially isotropic composite laminates can be attained by following the lay-up patterns illustrated in Figs. 5B and 5C.
  • Fig. 5B a plurality of sheets 58 (diagonally oriented fibers) are laid up so that the direction of fiber orientation of each sheet is at a 90 degree angle to the direction of fiber orientation of the sheet on either side thereof.
  • the fiber direction in every other sheet is plus 45 degree (with respect to the lengthwise edges) and the fiber direction in the alternate sheets is minus 45 degree.
  • This pattern carries throug lay-up 60B and in the composite laminate produced therefrom.
  • 5C shows a lay-up pattern which utilizes the plurality of sheets 56, with the fibers extending lengthwise (O degree) in every other sheet and cross-wise (90 degree) in the alternating sheets. This pattern carries into the lay-up 60C and the composite laminate produced therefrom.
  • the composite laminates produced from lay-ups 6OB and 60C are essentially isotropic, since the reinforcing fibers 20 therein extend in two mutually perpendicular directions.
  • Lay-ups 60, 60A, 60B and 60C are shaped under heat and pressure, preferably by compression molding, as shown diagrammatically in Fig. 6.
  • the preferred apparatus for forming composite laminates 10 or 10A is a conventional compression mold 70.
  • Such mold may comprise a stationary lower platen 72 having an upwardly extending mold cavity member 74 mounted thereon, and a vertically reciprocable upper platen member 76 having a mold cavity member 78 extending downwardly therefrom. Mold cavity member 74 and 78 are of mating shape.
  • a lay-up 60, 60A, 60B or 60C is placed in the lower mold cavity member 74.
  • the upper mold cavity member is lowered to molding position, and heat and pressure are applied.
  • the molding temperature is above the glass transition temperature or melting point of the matrix polymer but below the melting point of the LCP, so that the LCP fibers in individual layers do not disintegrate during processing.
  • a suitable molding temperature is about 260°C.
  • the molding pressure and time must be sufficient to cause consolidation of the lay-up into a coherent composite laminate.
  • the upper platen 76 is lifted and the composite laminate is allowed to cool to ambient temperature in the lower mold cavity 74. The cooled laminate is then removed and is ready for testing or use.
  • a mold having dies giving the desired shape are used in place of the conventional compression mold. Fibers in such composite will extend essentially uni-directionally if the lay-up pattern of Fig. 5 is used, and in different directions if any of the lay-up patterns of Figs. 5A, 5B or 5C is used.
  • the present invention provides high performance, high strength, high modulus and high temperature resistant fiber reinforced thermoplastic composites. While considerable success has been achieved previously in preparation of long fiber reinforced ther oset resins, success in making long fiber reinforced thermoplastic composites has been more limited.
  • the present invention provides long fiber reinforced thermoplastic composites and an economical process for preparing the same. Processing is considerably simplified by the fact that the reinforcing fibers are formed in situ rather than being formed separately in a previous operation and then encapsulated into a polymer matrix.
  • the process of this invention saves energy. Energy requirements are less than those required to form otherwise similar laminates containing preformed reinforcing fibers.
  • Composites of the present invention are particularly useful in the automotive, aircraft and marine industries. This is especially true of composites of this invention which are based on engineering thermoplastics such as PEEK and PEL In particularly, composites of this invention are useful in making automobile body parts and boat hulls. Other uses will be apparent to those skilled in the art.
  • EXAMPLE 1 This example describes the preparation of a composite laminate 10, having the fiber configuration shown in Fig. 1 (i.e., all fibers extending in the same direction).
  • This composite laminate consisted of 20 percent by weight of polyetherimide (the matrix polymer) and 80 percent by weight of a thermotropic liquid crystal polymer (LCP) .
  • the polyetherimide used is "Ulte" 1000, made by General Electric Company, Schenectady, New York. This is an amorphous polymer having a glass transition temperature of 215°C.
  • the liquid crystal polymer is "Vectra" A 950 distributed by Celanese Research Corp. of Summit, New Jersey. This polymer has a melting point of 275°C and is believed to consist essentially of about 25-27 mole percent of 6-oxy-2- naphthyl moieties and 73-75 mole percent of p-oxybenzoyl moieties.
  • Pellets of a PEI/LCP blend prepared according to U. S Patent No. 4,835,047 to Isayev, et al, are charged to the inlet of a Killion single screw extruder having a one inch barrel diameter.
  • This extruder is sold by Killion Extruders t Inc. of Riviera Beach, Florida.
  • This extruder has three heating zones 1-3 (zone 1 is near the feeder end) ; two heating zones 4 and 5 are in the region connecting the extruder and the die 32.
  • Die 32 has a single heating zone. All zones except number 4 are operated at 330°C; zone 4 is operated at 325°C.
  • the screw speed is 30 rpm.
  • a motor current of 4 amperes is used.
  • the pressure at the die entrance is 180 psi.
  • the melted blend is passed continuously from the screw extruder 30 to a coat hanger die 32.
  • This die has a heating jacket and a discharge slit 150 mm. x 1.5 mm.
  • Sheet 50 is extruded from die 32 at a speed of 4.5 in./min.
  • the extruded sheet 50 passes over rolls 34 and 36 and then through the nip of a pair of rolls 38.
  • the clearance between rolls 38 is 0.68 mm.
  • Rolls 38 are driven at a peripheral speed of 10 in./min., giving an extension ratio of 2.2. (This extension ratio is the ratio of peripheral speed of roll 38 to that of the sheet emerging from die 32) .
  • Sheet 50 is wound up on wind-up roll 40.
  • the long continuous prepreg sheet is cut into pieces approximately 4 inches. Eight of these pieces are laid up in the cavity of a compression mold so that the fibers in all pieces are oriented in the same direction (i.e., as shown in Fig. 5) .
  • the upper mold die member is lowered and heat and pressure (260°C, 1000 psi) are applied for one hour.
  • the mold is then opened and the composite laminate formed therein is removed after it has cooled to approximately ambient temperature. A laminate having a thickness of 0.106 inch is obtained.
  • the composite laminate samples are cut into narrow test strips 0.28 inch wide x 2.5 inch long x 0.106 inch thick.
  • the longitudinal direction of these test strips is the same as the fiber direction.
  • Tensile test at an elongation speed of 0.02 inch/min. shows a modulus of 13.8 GPa at 0.2 percent elongation in the fiber direction. It is not possible obtain a tensile strength (ultimate strength) result because the sample broke at the grips used to hold the sample ends for tensile testing.
  • Example 1 The procedure of Example 1 is followed except that the lay-up pattern shown in Fig. 5A is used. In this lay-up pattern, four fiber directions are used. The respective fiber direction angles in each layer from top to bottom in the mold cavity (measured from the longitudinal edge of the example to a line parallel to the predominant fiber direction) as follows: 0 degree, 45 degree, 90 degree, minus 45 degree, minus 45 degree, 90 degree, 45 degree, 0 degree.
  • a composite laminate as shown in Fig. 1A is obtained. The composite laminate thus obtained is tested in the same manner as the composite laminate obtained in Example 1.
  • a modulus at 0.2 percent elongation is 12.8 GPa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Un composite thermoplastique renforcé façonné, tel qu'un stratifié composite (10), comprend un polymère matriciel thermoplastique (22) ainsi qu'une pluralité de fibres longues (20) d'un polymère à cristaux liquides (PCL), lesquelles sont formées in situ dans le polymère matriciel. Ce composite est formé par transformation d'un préimprégné en une pluralité de feuilles ou de couches individuelles (12, 14, 16, 18) comprenant chacune des fibres longues (20) orientées de manière unidirectionnelle, dudit PCL dans une matrice (22) du polymère thermoplastique. On forme une superposition par découpage de chaque feuille ou couche individuelle en pièces, de sorte que le sens de l'orientation des fibres dans chacune desdites pièces est soit parallèle à une paire de bords soit à des angles de 45° par rapport à chacun desdits bords. On façonne ladite superposition sous l'effet de chaleur et de pression afin de former le composite.
PCT/US1990/004463 1989-08-10 1990-08-08 Stratifie composite thermoplastique autorenforce WO1991001879A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US39212289A 1989-08-10 1989-08-10
US392,122 1989-08-10

Publications (1)

Publication Number Publication Date
WO1991001879A1 true WO1991001879A1 (fr) 1991-02-21

Family

ID=23549327

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/004463 WO1991001879A1 (fr) 1989-08-10 1990-08-08 Stratifie composite thermoplastique autorenforce

Country Status (3)

Country Link
US (1) US5275877A (fr)
AU (1) AU6172790A (fr)
WO (1) WO1991001879A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238638A (en) * 1990-08-16 1993-08-24 The University Of Akron Process for preparing a self-reinforced thermoplastic composite laminate
US5260380A (en) * 1992-01-23 1993-11-09 The University Of Akron Self-reinforced composite and process for preparing same
US5268225A (en) * 1990-08-16 1993-12-07 The University Of Akron Self reinforced thermoplastic composite laminate
US5567485A (en) * 1992-04-17 1996-10-22 Mazda Motor Corporation Molding composite composition and method for molding the same
EP2335920A1 (fr) * 2008-09-29 2011-06-22 Kuraray Co., Ltd. Stratifié moulé résistant aux chocs, procédé de fabrication et matériau résistant aux chocs
WO2018121856A1 (fr) * 2016-12-28 2018-07-05 Kordsa Teknik Tekstil Anonim Sirketi Composite thermoplastique renforcé de fibres

Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3343381B2 (ja) * 1992-12-25 2002-11-11 住友化学工業株式会社 長繊維強化ポリオレフィン樹脂構造体からなる成形品
US6106274A (en) * 1995-08-30 2000-08-22 The Budd Company Molding apparatus with charge overflow
US5753164A (en) * 1995-08-30 1998-05-19 The Budd Company Automated thermoset molding method
US5846356A (en) * 1996-03-07 1998-12-08 Board Of Trustees Operating Michigan State University Method and apparatus for aligning discontinuous fibers
US6786420B1 (en) 1997-07-15 2004-09-07 Silverbrook Research Pty. Ltd. Data distribution mechanism in the form of ink dots on cards
US5997983A (en) * 1997-05-30 1999-12-07 Teledyneindustries, Inc. Rigid/flex printed circuit board using angled prepreg
CA2294331A1 (fr) * 1997-07-09 1999-01-21 Richard Robert Soelch Melanges polymere liquide cristallin-poly(phenylene oxyde)
US6618117B2 (en) 1997-07-12 2003-09-09 Silverbrook Research Pty Ltd Image sensing apparatus including a microcontroller
US6948794B2 (en) 1997-07-15 2005-09-27 Silverbrook Reserach Pty Ltd Printhead re-capping assembly for a print and demand digital camera system
US6985207B2 (en) * 1997-07-15 2006-01-10 Silverbrook Research Pty Ltd Photographic prints having magnetically recordable media
US6624848B1 (en) 1997-07-15 2003-09-23 Silverbrook Research Pty Ltd Cascading image modification using multiple digital cameras incorporating image processing
AUPO802797A0 (en) * 1997-07-15 1997-08-07 Silverbrook Research Pty Ltd Image processing method and apparatus (ART54)
US6879341B1 (en) 1997-07-15 2005-04-12 Silverbrook Research Pty Ltd Digital camera system containing a VLIW vector processor
AUPO850597A0 (en) * 1997-08-11 1997-09-04 Silverbrook Research Pty Ltd Image processing method and apparatus (art01a)
US6690419B1 (en) * 1997-07-15 2004-02-10 Silverbrook Research Pty Ltd Utilising eye detection methods for image processing in a digital image camera
US7110024B1 (en) 1997-07-15 2006-09-19 Silverbrook Research Pty Ltd Digital camera system having motion deblurring means
AUPO801997A0 (en) 1997-07-15 1997-08-07 Silverbrook Research Pty Ltd Media processing method and apparatus (ART21)
DE69943330D1 (de) * 1998-02-23 2011-05-19 Draka Comteq Bv Verbundbauelemente mit thermotropem flüssigkristallinem Polymer Verstärkung für faseroptische Kabel
US6264454B1 (en) 1998-03-11 2001-07-24 The Budd Company Wrapped SMC charge method and apparatus
US6103150A (en) * 1998-03-11 2000-08-15 The Budd Company Molding overflow feedback method
AUPP702098A0 (en) 1998-11-09 1998-12-03 Silverbrook Research Pty Ltd Image creation method and apparatus (ART73)
CA2355257A1 (fr) * 1999-01-08 2000-07-13 E. I. Du Pont De Nemours And Company Compositions a base de melanges de polymeres cristallins liquides poly(phenylene oxydes) a indice de cheminement d'arc eleve
AUPQ056099A0 (en) * 1999-05-25 1999-06-17 Silverbrook Research Pty Ltd A method and apparatus (pprint01)
BR0015244B1 (pt) * 1999-11-03 2010-05-04 "estrutura compósita elástica".
US6682802B2 (en) * 2000-12-14 2004-01-27 Intel Corporation Selective PCB stiffening with preferentially oriented fibers
US20030118836A1 (en) * 2001-10-24 2003-06-26 Lee Jeong Chang Fluoropolymer laminates and a process for manufacture thereof
JP3631994B2 (ja) * 2001-11-29 2005-03-23 旭ファイバーグラス株式会社 長繊維強化熱可塑性樹脂シートおよび該シートにより補強された複合成形体
TW200303354A (en) * 2002-02-05 2003-09-01 Sumitomo Chemicalco Ltd Anisotropic film and LCD using the same
AU2003219894A1 (en) * 2002-02-26 2003-09-09 Uni-Pixel Displays, Inc. Enhancements to optical flat panel displays
US7560400B2 (en) * 2003-07-16 2009-07-14 Raytheon Company Radome with polyester-polyarylate fibers and a method of making same
US20050024289A1 (en) * 2003-07-16 2005-02-03 Fredberg Marvin I. Rigid radome with polyester-polyarylate fibers and a method of making same
US7459200B2 (en) * 2003-08-15 2008-12-02 Intel Corporation Circuit board design
ES2260998B2 (es) * 2004-03-26 2007-06-01 Universidad Politecnica De Madrid Metodo de moldeo por compresion de termoplasticos reforzados.
US7379642B2 (en) 2005-01-18 2008-05-27 Adc Telecommunications, Inc. Low shrink telecommunications cable and methods for manufacturing the same
US8377543B2 (en) * 2006-11-10 2013-02-19 Nec Corporation Multilayer-wired substrate
WO2009014486A1 (fr) * 2007-07-23 2009-01-29 Sandvik Intellectual Property Ab Produit en un matériau à résistance élevée
US20090228463A1 (en) * 2008-03-10 2009-09-10 Cramer Richard D Method for Searching Compound Databases Using Topomeric Shape Descriptors and Pharmacophoric Features Identified by a Comparative Molecular Field Analysis (CoMFA) Utilizing Topomeric Alignment of Molecular Fragments
US8391658B2 (en) 2008-05-28 2013-03-05 Adc Telecommunications, Inc. Fiber optic cable with jacket embedded with reinforcing members
US8107781B2 (en) 2009-11-20 2012-01-31 Adc Telecommunications, Inc. Fiber optic cable
WO2011143401A2 (fr) 2010-05-14 2011-11-17 Adc Telecommunications, Inc. Dispositif d'enceinte d'épissure pour câbles de fibre optique
US8885998B2 (en) 2010-12-09 2014-11-11 Adc Telecommunications, Inc. Splice enclosure arrangement for fiber optic cables
TWI516373B (zh) * 2014-01-17 2016-01-11 三芳化學工業股份有限公司 硏磨墊、硏磨裝置及製造硏磨墊之方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4728698A (en) * 1985-09-06 1988-03-01 University Of Akron Liquid crystal fiber-reinforced polymer composite and process for preparing same
US4820568A (en) * 1987-08-03 1989-04-11 Allied-Signal Inc. Composite and article using short length fibers
US4835047A (en) * 1987-05-14 1989-05-30 Avraam Isayev Wholly aromatic polyester fiber-reinforced polyetherimide composite and process for preparing same

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4468364A (en) * 1983-04-28 1984-08-28 Celanese Corporation Process for extruding thermotropic liquid crystalline polymers
US5006402A (en) * 1989-04-28 1991-04-09 The University Of Akron Wholly aromatic polyester fiber-reinforced high performance thermoplastic and process for preparing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4728698A (en) * 1985-09-06 1988-03-01 University Of Akron Liquid crystal fiber-reinforced polymer composite and process for preparing same
US4835047A (en) * 1987-05-14 1989-05-30 Avraam Isayev Wholly aromatic polyester fiber-reinforced polyetherimide composite and process for preparing same
US4820568A (en) * 1987-08-03 1989-04-11 Allied-Signal Inc. Composite and article using short length fibers

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238638A (en) * 1990-08-16 1993-08-24 The University Of Akron Process for preparing a self-reinforced thermoplastic composite laminate
US5268225A (en) * 1990-08-16 1993-12-07 The University Of Akron Self reinforced thermoplastic composite laminate
US5260380A (en) * 1992-01-23 1993-11-09 The University Of Akron Self-reinforced composite and process for preparing same
US5567485A (en) * 1992-04-17 1996-10-22 Mazda Motor Corporation Molding composite composition and method for molding the same
EP2335920A1 (fr) * 2008-09-29 2011-06-22 Kuraray Co., Ltd. Stratifié moulé résistant aux chocs, procédé de fabrication et matériau résistant aux chocs
EP2335920A4 (fr) * 2008-09-29 2012-09-12 Kuraray Co Stratifié moulé résistant aux chocs, procédé de fabrication et matériau résistant aux chocs
WO2018121856A1 (fr) * 2016-12-28 2018-07-05 Kordsa Teknik Tekstil Anonim Sirketi Composite thermoplastique renforcé de fibres

Also Published As

Publication number Publication date
US5275877A (en) 1994-01-04
AU6172790A (en) 1991-03-11

Similar Documents

Publication Publication Date Title
WO1991001879A1 (fr) Stratifie composite thermoplastique autorenforce
US5268225A (en) Self reinforced thermoplastic composite laminate
US5260380A (en) Self-reinforced composite and process for preparing same
US6277773B1 (en) Polymeric materials
US5238638A (en) Process for preparing a self-reinforced thermoplastic composite laminate
EP0217563B1 (fr) Composite de polymère renforcé de cristal liquide fibreux et procédé pour sa préparation
EP1015242B1 (fr) Composites de papier multicouche
CA1327689C (fr) Pellicules polymeriques a orientation multiaxiale, et methode pour leur preparation
US4892774A (en) Interleafed fiber-reinforced thermoplastic composite
US6017834A (en) Monoliyhic polymeric product
EP0291323B1 (fr) Composite de polyétherimide renforcé par des fibres de polyester aromatique et méthode de préparation
KR100684815B1 (ko) 1축 또는 2축-연신된 폴리에스테르 수지 발포 재료
KR100230025B1 (ko) 섬유 강화 다공성 시이트
EP0543953B1 (fr) Composite autorenforce de polymeres de cristaux liquides thermotropiques
US5032433A (en) Thermoplastic web and process for manufacture same
EP0330960A2 (fr) Procédé de formation d'articles thermoplastiques renforcés avec des fibres
Alfey Jr et al. Multipolymer systems
US4614629A (en) Rotational compression process for forming liquid crystalline polymers with ultra-high mechanical properties
EP0354285A1 (fr) Procédé de fabrication de pellicules orientées uniaxialement
US5006403A (en) Wholly aromatic polyester fiber-reinforced poly(phenylene oxide) and process for preparing same
EP0646141B1 (fr) Thermoplastiques extrudes, polymeres a cristaux liquides et leurs melanges possedant une structure plane
WO1988001633A1 (fr) Melange polymere a base de polyalkylenephtalate
US5283114A (en) Wholly aromatic polyester fiber-reinforced polystyrene-poly(phenylene oxide) blend
JPH0832499B2 (ja) 転写フィルム用耐熱ポリエステルフィルム
JPS62116666A (ja) 自己強化重合体複合物及びその製法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE

NENP Non-entry into the national phase

Ref country code: CA